We report on XANES and EXAFS measurements of SmNiO 3 from 20 K to 600 K and up to 38 GPa at the Ni K-and Sm L 3 -edges. A multiple component pre-Ni K-edge tail is understood originating from 1s transitions to 3d-4p states while a post-edge shoulder increases distinctively smooth, at about the insulator to metal phase transition (T IM ), due to the reduction of electron-phonon interactions as the Ni 3d and O 2p band overlap triggers the metallic phase. This effect is concomitant with pressure induced Ni-O-Ni angle increments toward more symmetric Ni 3+ octahedra of the rhombohedral R¯3c space group. Room temperature pressure dependent Ni white line peak energies have an abrupt ~3.10±0.04 GPa Pa valence discontinuity from non-equivalent Ni 3+δ + Ni 3-δ charge disproportionate net unresolved absorber turning at ~T IM into Ni 3+ of the orthorhombic Pbnm metal oxide phase. At 20 K the overall white line response, still distinctive at T IM ~8.1±0.6 GPa is much smoother due to localization. Octahedral bond contraction up to 38 GPa and at 300 K and 20 K show breaks in its monotonic increase at the different structural changes. The Sm L 3 -edge does not show distinctive behaviors either at 300 K or 20 K up about 35 GPa but the perovskite Sm cage, coordinated to eight oxygen atoms, undergoes strong uneven bond contractions at intermediate pressures where we found coexistence of octahedral and rhombohedral superexchange angle distortions. We found that the white line pressure dependent anomaly may be used as an accurate alternative for delineating pressure-temperature phase diagrams. Pacs number(s): X-ray absorption spectra--78.70.Dm High-pressure effects in solids and liquids--62.50.-p; Crystallographic aspects of phase transformations--61.50.Ks (Pressure treatment--81.40.Vw) Metal-insulator transitions and other electronic transitions--71.30.+h; Strongly correlated electron systems--71.27.+a